Sulfonated dihalogeno diaminostilbenes



Patented Sept. 7, 1954 SULFONATED DIHALOGENO DIAMINO- STILBENES DeltonW. Hein, Somerville, N. J., and Wyvona A. Lane, Washington, D. 0.,assignors to American Cyanamid Company, New York, N. Y., a

corporation of Maine No Drawing. Application July 17, 1951, Serial No.237,298

7 Claims. 1

The present invention concerns a new series of acylatedhalogeno-stilbene compounds useful as morescerit brighteners and theirproduction. More specifically they constitute sulfonic acids andsulfonates of compounds of the general for mula in which R is theresidue of an acylating agent, attached to the amino nitrogen by acarbon to nitrogen bond; Hal is a halogen radical, preferably chlorine;and the sulfonic or sulfonate substituents may be in the stilbenenucleus or in the R grouping or both.

It is often convenient to isolate and use these sulfonic acids in theform of their ammonium or alkali metal salts, and these salts are meantto be included, as obvious equivalents, whenever the compounds arementioned.

These brighteners combine to an extraordinarily high degree thedesirable properties of fluorescent power, aflinity, hypochloriteresistance, and freedom from tendency to discolor either detergents orfabrics. In the past, in preparing brighteners, it has generally beennecessary to compromise on certain of these qualities. This has beenparticularly true of hypochlorite bleach resistance and discoloration ofdetergents, whichare particularly weak points with ordinary brightenersof the diaminostilbenedisulfonic acid type.

The brighteners of the present invention, however, are quite free fromthese drawbacks. They show not only a high degree of affinityandfluorescent power but are surprisingly free from any tendency todiscolor either detergents or fabrics. They also have an excellenthypochlorite fastness, so that they can be applied before or during thebleaching operation without any difficulty.

The compounds of the present invention can be prepared by differentmethods depending on the sulfonating operation. The latter may becarried out either before or after acylation. For example, to obtainproducts sulfonated in the stilbene nucleus, adichlorodiaminostilbenedisulfonic acid, such as those disclosed andclaimed in the copending application of Lane and Hein for U. S. LettersPatent, Serial No. 237,305, filed of even date, can be reacted, eitherin an aqueous or anhydrous medium, according to known methods, with anacylating agent.

It is an advantage of the present invention that a very wide variety ofacylating agents may be used. Examples of such acylating agents areanhydrides such as acetic anhydride, maleic anhydride, and phthalicanhydride; acid halides such as butyryl chloride, trifluoroacetyl chlo-V ride, adipyl chloride, crotonyl chloride, ethoxyacetyl chloride,benzoyl and phenylacetyl chloride and the alkyl, halo, nitro, amino, andoxygenated substitution products thereof, the naphthoyl chlorides,z-hydroxy 3 naphthoyl chloride, phenoxyacetyl chloride, cinnamoylchloride, diethyl carbamyl chloride, hydrocinnamoyl chloride,hexahydrobenzoyl chloride, cyclohexylacetyl chloride, furoyl chloride,nicotinyl chloride, picolinyl chloride, and thiophene alpha carboxylicacid chloride; substituted carbamyl chlorides and related carbamic acidderivatives such as the phenyl and naphthyl isocyanates andisothiocyanates; heterocyclic acylating agents such as cyanuric chlorideand chloropyrimidines. Residual active halogen in the last mentionedbifunctional or trifunctional acylating agents can then be replaced bysubstituted amino or oxy groups, such as anilino, phenoxy, and the like.

Particularly valuable products are given by acylating with chlorides ofbenzoic acid and its substitution products, especially the loweralkoxysubstitution products, such as the isomeric anisic and ethoxybenzoicacids, 2,5-dimethoxybenzoic acid, o-propoxybenzoic acid,o-ibutoxybenzoic acid, 2,4-diethoxybenzoic acid, Z-methoxy 3methylbenzoic acid, p-butoxybenzoic acid, 3-ethoxy-4-methoxybenzoicacid, 3,4,5-triethoxybenzoic acid, 2,4,5-trimethoxybenzoic acid,4-methyl-2-ethoxybenzoic acid, and the like. With these alkoxy-benzoicacids, particularly the polyalkoxy derivatives, the acylation is bestcarried out in an anhydrous solvent solution. Anhydrous pyridine, forexample, is an excellent solvent because of the sensitivity of theseacid chlorides to hydrolysis. These products constitute a preferredembodiment of the present invention.

It is equally possible to obtain products which are sulfonated, not inthe stilbene nucleus, but in the portion of the molecule represented byR in the above formula. This can be done by reacting adichlorodiaminostilbene with an aromatic acylating agent, such as one ofthose mentioned above, and then sulfonating the product.

Utilization of the compounds of this invention' is not limited totreatment of any particular fibers, they being useful with both animaland vegetable fibers and synthetic fibers such 3 as rayon. Celanese,nylon. and the like. Nor are they limited to'tre'atment of textilefabrics. They may also be beneficially used in the manufacture of paperand felt products, transparent or translucent sheets or pellicles ofcellulose, and white or light colored leathers and the. like. Theirusefulness also extends to mutually compatible varnishes, plasticcoatings, and white or colored plastic shapes. They have a particularlygood afiinity and compatibility with amino-plast resins.

The following examples will illustrate a number of the procedures whichcan be used to obtaln these compounds, and will give further informationas to their properties. All parts are by weight and temperatures indegrees Centigrade unless otherwise specified.

Ewample 1 CONE CH=CH Gil resulting 2,4 dimethoxybenzoyl chloride isadded to a slurry of 4.4 parts of 5,5-dichloro-4,4-diaminostilbene-2,2'-disulfonic acid in 147 parts of pyridine. Themixture is refluxed until acylation is complete and then worked up inthe manner described in the preceding example. A high yield of very paleyellow solid is obtained.

This product is a brightener of excellent properties. Its high strengthis still further increased by its unusual degree of affinity; forexample, at concentrations of 0.25%, it is approximately 50% strongerthan the bis-(2,4-dimethoxybenzoyl) derivative of4,4-diaminostilbene-2,2-disulfonic acid. It is also of outstandingbleach fastness, losing only 18% of its strength in a hypochlorite bathunder conditions that destroy 60% of the strength of the above mentioneddiaminostilbenedisulfonic acid compound.

OCzHt Example 3 A mixture of parts of5,5'-dichloro-4,4-diamino-stilbene-2,2'-disulfonic acid and 735 parts ofdry pyridine is stirred and refluxed and gradually treated with 37.6parts of o-ethoxybenzoyl chloride. Refluxing and stirring are continueduntil free primary amino groups are no longer present. The reactionmixture is drowned in approximately 700 parts of water, together withenough sodium carbonate to give a weakly alkaline reaction. Twenty partsof salt are added and the solution is steam-distilled to remove thepyridine. The residual slurry is filtered at room temperature, washedwith 2% salt solution, and dried at 100. An excellent yield of verylight cream-colored solid is obtained.

This product has outstanding qualities as a brightenen-conferring strongbluish fluorescence upon cotton cloth from dilute water or soapsolution. It is readily incorporated in soap or synthetic detergentswithout effect on their appearance. It is particularly noteworthy forits resistance to hypochlorite bleach; for example, in one test it losesonly 15% of its strength while, under the same conditions, thebis-o-ethoxybenzoyl derivative of 4,4-diaminostilbene-2,2'- disulfonicacid, which is a substantially weaker brightener to begin with, loses60% in strength.

Example 2 OCH:

A mixture of 10.9 parts of 2,4-dimethoxybenzoic acid and 9 parts ofthionyl chloride is allowed to react at room temperature, excess thionylchloride then being removed by evacuation. The

32.8 parts of di-o-tolylguanidine is dissolved in 88.5 parts of watercontaining 13.6 parts of concentrated hydrochloric acid. The resultingsolution is filtered and diluted to the volume of. 250 parts of water.

7.3 parts of 5,5-dichloro-4,4-diaminostilbene- 2,2'-disulfonic acid isdissolved in 50 parts of water by the addition of just sufiicient 5Nsodium hydroxide to give a clear solution. This is gradually added to asolution of 18.5 parts by volume of the above prepareddi-o-tolylguanidine hydrochloride solution and 25 parts of water. Therebenzene, slurried in 200 parts of water, containing 10 parts of salt,and steamed free of nitrobenzene. The product, obtained as disodiumsalt, is then filtered, washed with dilute sodium carbonate solution,followed by water, and dried at C. It is a fine pale yellow crystallinesolid of excellent properties as a brightener.

Example 4 I CMMONH WHG 4.4 parts of5,5-dichloro-4,4'-diaminostilbenecomplete, and worked up as describedabove. A 2,2-disulfonic acid is slurried in 100 cc. of water very highyield of light yellow product is ohand treated with just enough sodiumcarbonate tam d, to effect solution. The resulting solution is heated to40 0. and treated gradually with 4.8 Emmpze 8 SOaH B0111 0.0m wagmgc.

1 c1 parts of phenyl isocyanate. After prolonged A mixture of 2.6 partsof 5,5'-dichloro-4,4'-distirring, the mixture is treated with anadditional aminostilbene-2.2'-disu1fonic acid and 5.3 parts 100 parts ofwater and heated to 90 C. It is then of 4-chlorobenzoyl chloride in 98parts of dry pyricooled and filtered. The cake is washed with 16 dine isreacted and worked up substantially as 2% salt solution and dried at 100C. The proddescribed in the preceding examples. An exceeduct is a whitesolid with excellent brightener ingly high yield of product is obtainedin the form properties. 4 of a white solid.

Example 5 Emample 9 son: soar 2 80:15 SOaH O|H;CONH CH: CH NHOOCcH; H oH'CONHQCBHCHQNHOOH 0 H 1 l l l A slurry of 4.4 parts of5,5'-dichloro-4,4'-di- The procedure of the preceding examples isamino-stilbene zz'-disulfonic acid and 147 parts used to react 4.4 partsof 5,5'-dichloro-4,4-diof dry pyridine is stirred and refluxed andgraduaminostilbene-2,2'-disulfonic acid and 7.8 parts ally treated with8.4 parts of benzoyl chloride. of furoyl chloride in 147 parts of drypyridine. Stirring and heating are continued until acyla- The product isobtained in the form of a white tion is complete, as shown by absence ofprimary solid. amino groups. The reaction mixture is then Example 10808E SOiH CaHsOCHr-CONH CH CH NHCOCHiOCtHt drowned in approximately 200parts of water. The procedure of the preceding examples is used madeweakly alkaline with sodium carbonate. to react 4.4 parts of5,5'-dichloro-4,4'-diaminoand freed of pyridine by steam distillation.The stilbene-2,2-disulfonic acid and 10.2 parts of product, in the formof its disodium salt, is 'filphenoxyacetyl chloride in 147 parts of drypyritered, washed with parts of 2% salt solution. dine. The product isobtained as a white solid.

followed by 50 parts of ice water, and dried at C. Example 11 0 CH5 SOIHSOaH 0 C515; Gangs. CHQNHO 1 01 Example 6 12.8 parts of o-phenoxybenzoicacid is converted S033 803K to acid chloride by refluxing with thionylchloride,

excess of the latter then being removed by dis- CHaCsH4CON'H CHzCHNHCOCQHiCH-I tillation at reduced pressure. The product is I reactedwith 4.4 parts of 5,5'-dichloro-4,4'-di- 1 1aminostilbene-2,2'-disulfonic acid in 147 parts of The procedure of thepreceding example is dry pyridine, according to the procedure of thefollowed, except that the benzoyl chloride is repreceding examples. Anexcellent yield of pale placed by 9.27 parts of mixed isomeric toluylyellow product is obtained. chlorides. The disodium salt of product isobtained in excellent yield as a light yellow solid. Example 12 soussols omen: CHCH: cH-o ONHQCH OHQNHCOCH CHCH: oHcm 1 1 Example 7 Theprocedure of the preceding examples is used SOaH A mixture of 2.2 partsof 5,5-dichloro-4,4-dito react 4.4 parts of5,5'-dichloro-4,4'-diaminoaminostilbene-2,2-disulfonic acid and 2.9parts stilbene-2,2'-disulfonic acid and 7.8 parts of sorofbeta-naphthoyl chloride in 98 parts of dry boyl chloride in 147 parts ofdry pyridine. An pyridine is stirred and refluxed until acylation isexcellent yield of product is obtained.

0 l o I 7 Example .13

130B: SOIH 11.9 parts of o-phenylbenzoic acid is converted to acidchloride by treatment with thionyl chloride, followed by distillationunder reduced pressure to remove the excess. The acid chloride isreacted, as described in the preceding examples, with 4.4 parts of5,5-dichloro-4,4'ediaminostilbene-2,2'-disulfonic acid in 147 parts ofdry py idine. vA very good yield .of product is obtained.

Example 1 4 CuHa A slurry of 1.1 parts of6,6'-dichloro-4,4'-diaminostilbene-2,2'-disulfonic acid in 74 parts ofdry pyridine is heated to the boil and treated with a solution of 2.0parts of 2,4-dimethoxybenzoyl chloride in 5.5 parts of drychlorobenzene. When acylation is complete, the solution is poured into50 parts of water containing 1.1 parts of sodium carbonate and 5 partsof salt. After steam distillation, the residual solution is cooled .sQl(CzB-ahN-OCONHQCH on New-Grimm.

7.14 parts of purified thionyl chloride is slowly added, with stirring,to 147 parts of dry pyridine. To this .is slowly added 11.6 .parts ofp-diethylaminobenzoic acid. The solution is stirred for a short time .at45 C. and {then treated .with .44

parts of 5,5'-dichloro-4,4-diaminostilbene-2,2- disulfonic acid.Acylation is completed under reflux and the reaction drowned into 150parts of water containing enough sodium carbonate to give a weaklyalkaline mixture. The pyridine is removed by steam distillation. Theproduct, a pale yellowsolid, is filtered at room temperature, washedwith 2% salt solution, and dried at 100.

Example 15 OCzH vSOiH SOaH .A :mixtureof 1.5 parts of:6.6'-dichloro- 4,4diaminostilbene-'2,2-disulfonic acid and :98 parts of ry pyridine isheated to the boiland gradually treated with 2.4 parts ofo-ethoxybenzoyl chloride. Refiuxing is continued until vfree aminogroups are no longer detectable. The reaction mixture and filtered. Theproduct is washed with 2% salt solution and dried at 100 C. It isobtained in excellent yield.

Example 1 7 S 03H SOaH ClHtO reflux. The mixture .is then added to 300parts of water containing 10 parts of salt and 5.3 parts of sodiumcarbonate. The pyridine is removed by steam distillation, and theproduct crystallized on cooling. It is filtered and dried.

Example 18 soin cum-GeomzQ-cn z-GHQNHC 000 CH: 1 cl Example 16 OCH: SOaHBOSH 011,0 'CONH Amixture of 11.2 parts of 2,2'-dichloro-4,4-diaminostilbene and 110 parts of chlorobenzene is heated to the boil andtreated with 16.3 parts of anisoyl chloride. Thisisfollowed by 6.2 partsof pyridine, stirring under reflux being continued until acylation iscomplete. The reaction mixture .is steam-stripped and filtered .hot. Theproduct is washed with .hot water and .dried at 9 10 50 C. Aquantitative yield of 4,4'-dianisoyl- 2. A sulfonated dihalogenodiaminostilbene amino-2,2'-dichlorostilbene is obtained. having theformula 6.4 parts of the above prepared product is addsox ed over aperiod of one-half hour to 27.2 parts of chlorosulfonic acid at atemperature below 5 C. 5 RNH 4 NEW After three hours at 0-5 C., thereaction mixture is poured on excess ice. The resulting so- 01 C] iggzifiggfi gg g fi agzg concentration and in which R and R are aromaticcarboxylic acyl radicals and X is selected from the group con- Example19 sisting of H, NH4 and the alkali metals.

' SOaH 50:11

N N CSHINH NHQCH on NH-f TNHCBHI N N 01 I N N NHCQHL NHCaHs A slurry of4.4 parts of 5,5'-dichloro-4.4'-di- 3. A sulfonated dihalogenodiaminostilbene aminostilbene-2,2'-disulfonic acid in 90 parts of 20having the formula water is dissolved by the addition of just enough 10%aqueous sodium carbonate to give a weakly alkaline solution. Theresulting solution is cooled to 0 and slowly treated at this tempera-RCONHQCELCHCDNHCOR ture with a solution of 3.7 parts of cyanuric'chloride in 63 parts of acetone. The acidity is adjusted as necessaryby periodic addition of in which R and R are carbocyclic aromatic radi-10% sodium carbonate solution. When free cals of less than three ringsand X is selected amino groups are no longer detectable in the from thegroup consisting of H, NH4 and the solution, 18.6 parts of aniline areadded, and the alkali metals.

mixture is heated to the boil. Distillation is con- 4. A sulfonateddihalogeno diaminostilbene tinued until the boiling point reaches 99 C.,the having the formula SOaX SOiX CONH CH=CH NHOC AlkO OAlk C1 01 A1110OAlk distillate being replaced by the gradual addiin which Alk is alower alkyl radical and X is setion of 100 parts of water to themixture. Again 40 lected from the group consisting of H, NH; and 18.6parts of aniline are added, and the mixture the alkali metals.

refluxed for minutes. The product is filtered 5. A sulfonated dihalogenodiaminostilbene at room temperature, washed with 2% salt soh ving theformula lution and dried at 100. A very high yield of OAR 0A1]: productis obtained. It has excellent brightener 4 characteristics. CONH GH=CHNHO c We claim: 1. A sulfonated dihalogeno diaminostilbene 1 1 havingthe formula in which Alk is a lower alkyl radical and X is sesoix). soaxlected from the group consisting of H, NH; and

the alkali metals. RNH CH=CH NHR' 6. A sulfonated dihalogenodiaminostilbene having the formula v C1 C1 soix solx wherein R andl-tare acyl radicals selected from RNH CH=CH the group consisting oforganic carbozqlhc acyl radicals, symmetrical triazinyl radicals, andthe c1 01 radical R"NH-C=O in which R" is an carbo- 6o cyclic aromaticradical of less than three rings; In which R and are symmetricaltl'iazinyl x is selected from the group consisting of H, radicals and Xi selected from the group c NH4, and the alkali metals; n is an integerof not i ting of H, NH: and the alkali metals. more than one and therebeing at least one sul- A S O t d dihalogenO infls ilbene fonatesubstituent on R or R. when n is zero; vi h formula NHCcHu NHCuH;

11 and X is selected from the group consisting of Number H, NH; and thealkali metals. 2,468,431 2,580,234 References Cited in the file of thispatent 2,581,057 UNITED STATES PATENTS 5 2,581,059

Number Name Date 2,376,743 Wendt May 22, 1945 112 Name Date Eberhaxt eta1 Apr. 26, 1949 Lecher et al. Dec. 25, 1951 Wirth et a1. Jan. 1, 1952Witte Jan. 1, 1952 OTHER REFERENCES Berichte, vol. 46 pp. 1235-6 (I913).

1. A SULFONATED DIHALOGENO DIAMINOSTILBENE HAVING THE FORMULA